Recovery of valuable hydrocarbons



Dec. 7, 1943.

RECOVERY OF VALUABLE HYDROCARBONS i, FE;

Filed Oct. 26, 1959 Am www@ Qecanaiy .4 l E Z/ ./415 Q im Patented Dee. 7, 1943 2,335,855

RECOVERY F VALUABLE HYDROCARBONS Edwin L. Hall, Philadelphia, Pa., assigner to The United Gas Improvement Company, acorporation oi Pennsylvania v Y Application october 26, 1939, serial No. 301,323y`v 3 Claims.

This invention pertains generally to the recovery of valuable hydrocarbons from gas mixtures containing them.

The invention pertains more particularly to the Another object is to eiect such a recovery in a system which is simple in arrangement and operation.

With these and other objects in view myinvention is based in partl upon a two-stage scrubbing recovery of such hydrocarbons from a manufacsystem in which a relatively low molecular weight tured gas obtained by the pyrolytic decomposiand consequently relatively volatile scrubbing tion oi' hydrocarbon oil with or without the aid medium is used in the ilrst stage toremove'more oi' catalysts. volatile compounds such as benzene, C4 and Cs A Various processes for the manufacture of artihydrocarbons from the gas and a higherfmolecuficial gases'such as carburetted water gas and oil` m lar Weight and consequently less volatile scrub-,-I gas wherein a petroleum oil is decomposed pyrobing medium is used in a second stage to remove lytically o'r catalytically (or both) result in gas vapors of the relatively'more volatile scrubbing mixtures which contain difllcultly condensible medium from the residual gas. gaseous decomposition products such as methane, I have found that my two-stage system may be ethane, ethylene, propylene, etc., as well as some made very effective by the use of toluene substanhydrogen. There are also present the vapors of tially free from benzene as the relatively low momore easily vcondensible hydrocarbonsubstanees lecular weight scrubbing medium in the rst which may be more or less readily separated from stage and a relatively high molecular weight; the gas mixtures. These latter substances comscrubbingmedium such as absorbent oil in the prise a source of valuable hydrocarbonsand parsecond stage. I iind that the principal objecticularly those of the resin-forming unsaturated tions to the use' of either of these two scrubbing type such as styrene, indene, methyl styrene, eymedia individually, namely 1) loss of low molecclopentadiene, isobutylene, isoprene, piperylene, ular weight scrubbing medium ldue tothe relabutadiene, etc. Y tively high vapor pressures thereof, even at con- To remove light oils from manufactured gases siderably lowered temperatures, 2) relatively one may use an absorbent oil as a scrubbing melarge quantities of high molecular weight absorb dium. The absorbent 'oil (also designated as ing/medium required, (3) difllulty in recovering wash oil") may be for instance a petroleum dispolymerizable hydrocarbon constituents associat-` tillate boiling in the range of about 400 to '100 ed with thehigh molecular weight absorbing me, F.. 1. e., about 205 to 370 C. The amount of 30 dium, (4) relatively high stripping temperatures such an oil required is proportional to its morequired with high molecular weight absorbing lecular weight. In some cases it has been /iound medium, ere Substantially Completely eliminated that in addition to suffering from the disadvanel by mYinVentiOn. f tage that a greater quantity is required than or, The invention may be further described in low molecular weight oils, the hydrocarbons that greater detail in COIlIleetiOn with the aecolnare being removed may become associated with Danying drawing, Which illustrates 011e preferred the high molecular weight absorbent oil in such a embedment thereof. Other ways of practicing manner as to render their subsequent removal my invention will suggest themselves to those extremely diflcult. i skilled in the art upon becoming familiar with It has been proposed tor use low molecular 40 the description herein. weight absorbent substances as the scrubbing Gas manufactured in any suitable gas-making medium 'but a common objection to the use oi' equipment (not shown) such as by e DIOeeSS insuch materials is that they possess relatively high v Lveolving the decomposition of hydrocarbon oil may vapor pressures and consequently the losses of` be passed through conventional or other conthe scrubbing medium in the gas may tend to bedensing equipment (nOt ShOWn) as iS CilStOIl'laryv excessive. in the art, in which substantial quantities of tar An 4object of my invention is the provision of a are separated and removed from the gas. By resystem for removing valuable relatively volatile duclng the temperature of the gasto say Just hydrocarbons (which may include the C4 and C5 Y above 0 C., the separation of substances such as unsaturated hydrocarbons) i'rom gas mixtures 60 indene, methyl styrene, styrene, and xylene is such as those from the source indicated, without substantially complete, and only a small partof objectionable loss of scrubbing medium yet with the toluene and a somewhat larger partof the good recovery of the major portion of the valuf benzene remain. On the yother hand, substanable hydrocarbon constituents of the gas. tially all of the hydrocarbons of iive'carbon at- 56 oms (called C5 hydrocarbons) and of four carbon ",way of conduit 5. I f' passed if desired to further vprocessing equipment atoms (called C4 hydrocarbons) remain in the 88.5.

To recover the rest of the benzene and substantial quantities of the C4 and C5 hydrocarbons, the gas may then be introduced by pipe I into a scrubbing tower 2 such as at the bottom,

in which towerit is contacted countercurrently with liquid toluene substantially free fromben'- zene which may be introduced at or near the top o1' the tower such as through pipe I2.

The toluene is contacted with the gas in a manner and under conditions capable of removlng substantially all the benzene and substantial quantities of the valuable C. and C5 hydrocarbons from the gas, the degree of removal being dependent upon the proportion of scrubbing medium to gas and the temperature at which scrub'- bing takes place.,

The gas leaves tower 2 by way of conduit 3. Due to the relativelyhigh volatility of toluene this gas will contain vapors thereof in an amount which, while not greatl relatively at the temperatures usually employed in tower 2,' represents'in` the aggregate a very substantial lossv of valuable toluene.

To recover'this toluene, thegas may be introduced by means of conduit 3 into a second scrub'- i bing tower 4f such as at the bottom. In this tower the gas containing vapors of the toluene is y contacted with-a relatively less volatile scrubbing medium illustrated for convenience as introduced at or near the top. As an example, an absorbent oil comprising a; petroleum oil fraction of the characteristics already mentioned such asv strawoil may be employed as the scrubbing medium in this secondaryscrubbing stage.

The relatively less volatile liquid scrubbing medium removes substantially'all the vapors [of v. the relatively more Volatile toluene from the gas which, as illustrated,I exits from the tower l by The residual gas may then be and then to storag/e for use as fuel,for i/ may be treated or used in any otherdesiredi'manner.

Returning. to the primary scrubbing tower 2v where the gasis initially treated accrding to my invention, the liquid toluene containing benzene sorbed vtoluene is separated and the less volatile `scrubbing medium is regenerated for reuse on fresh quantities of gas.

f :Such a recovery and regenerating zone may for instance be represented by any type of stripping still I4 into which the rich straw-oil may be introduced and-subjected to heat in order to separate the lower boiling constituents therefrom, by reason of diierences in. boiling points.A

It may be desirable to introducesteam as by pipe I5 to assist the separation.` The vapors of toluene and some vapors from the less volatile scrubbing medium (together with water Vapor, if steam isused), depending upon kthe sharpness of the separation obtained, leave the stripping zone by way of pipe I6 which then conducts them to equipment (not shown) for further separation and treatment. l

and C4 and Cs hydrocarbons .absorbed from the gas exits from the baseof the' tower through a suitably trapped conduit 6 and may be then introduced into a recovery and regenerating' zone wherein the absorbed materials are separated and recovered and the liquid toluene thus regenerated for reuse on fresh. quantities vof gas.

. Such a recovery and regenerating'zone may for instance comprise any convenient type of stripping still 1 into which the rich toluene may be .introduced and subjected to heat to ,effect the desired separation based upon differences in boiling points, in a well-known manner. If desired, and when expedient, steam or other vapor or gas may be introduced as Vby pipe 8 as a stripping medium to assist the separation. The vapors of the desired valuablehydrocarbons (together with the stripping medium if used, and some vaporsI of toluene-depending upon/ the sharpness of the separation obtainable in the stripping still) The lean scrubbing medium from which toluene has been removed may leave the stripping still I4 by way of pipe I'l which returns it through "a cooler I8 to inletIS, which serves to introduce it into the secondaryscrubber 4 for treatment of fresh quantities of gas. I

It `win thus be seenthat I attain the kobjects of my invention by the use of la simple land exible system involving two stages vof scrubbing.` Relatively efiicient absorption ratios. lare obtained,

since the more volatile toluene'is a more eillcient scrubbing mediumthan the less volatile petroleum oil fraction in about the inverseratio: of their molecular weights.

ratio is about 3 to 1.

My system permits of recovery of valuable hydrocarbons of the type indicated from gas with lowered polymerization losses-since substantially all `oi" the polymerizable `hydrocarbon bodies except possibly a small portion of butadienedependingupon the type; of operation-may be picked up in ther primary scrubber by the toluene from which'the low boiling hydrocarbons, such as ,C5s, `may be removed in a strippingv zone at# relatively low temperatures-that is,` low relative to the temperatures. that ywould be requiredv if a less volatile scrubbing medium `than toluene were to be employed. yGradual leave the stripping zone by way of vpipe 9 which conducts them-to equipment (not shown) for further separation and treatment.

The lean toluene from which the valuablehydrocarbons have beeny removed may leave the stripping zone by pipe I0 andows throughcooler Il to inlet pipe I2, which in turn introduces accumulations of high boiling resin formers such as styrene, indene, dicyclopentadiene, etc., which accumulate in the toluene in'- the Vprimary stripping zone'scrubbing circuit may be periodically removed as bottoms from the stripping still I by sending the toluene overhead. This may be accomplished at relatively low temperatures and with low reflux ratios, and if de- `sired yat reduced pressures to avoid polymerizing the bottoms.

The quantities of residual butadiene (C4 hydrocarbon) and `of residual C5 hydrocarbons recovered from the gas by the` relatively less volatile petroleum oil in the secondary scrubbing stage are usually too small to present any seriouspolymerization problem in the second stage scrub- In one particular'inf stance using toluene and-straw-oil, this inverse Hence, the bulk ,of the absorption work is done with a highly eillcient scrubbing medium. I l

" /,tion.

aaeaess bing and regenerating equipment. No appreciable amounts of high boiling polymerizable bodies such as styrene,-indene and dicyclopentadiene accumulate in the scrubbing oil and high strip'- ping temperatures are not required.

For the sake of simplicity, conventional apparatus elements such as necessary valves, pumps, meters, etc., have not been shown.

The scrubbing towers 2 and 4 may bev of any desired construction and operation for Velecting gas-liquid contact such as packed towers, vunpacked" towers, bubble-cap and -plate towers, sieve-plate tower, or the like.

ibing zone the scrubbed gas mixture containing vapors of toluene taken up by the gas from said` 5 scrubbing medium; contacting the scrubbed gas The separators 'I and I4 may lbe any suitable construction and operation such as stills. equipped with fractionating columns, if desired, and heated in any desired manner.

If preferred, one or both of separators 'I and I4 may be operated under partial vacuum thus permitting the stripping step to take place at correspondingly lower temperatures.

Coolers II and I8 may be of any suitablevtype, such as affords indirect heat-exchange with any suitable-cooling medium.' It may be preferred to maintain the recirculated scrubbing media entering the scrubbing towers 2 and 4 at I2 and I9 (respectively) at temperature at, or slightly condensation of any W er vapor contained in the gas ,which might adversely alect the scruby between the flowing nuid streams in any desired i manner to bring about greater heat economies;

as one instance, the liquid nowing in lines 6 and I3 might be passed through suitable heat-exchangers with the steam blowing in lines and i5 respectively.

'mixture in a secondary scrubbing zonewith a second liquid scrubbing medium relatively less volatile than said toluene to scrub out toluene vapors from said gas mixture by absorption thereof in saidvsecond liquid scrubbing medium; withdrawing from said second sbrubbing zone the residual gas mixture and th'e said relatively less volatile scrubbing medium containing toluene absorbed therein; and withdrawing from said primary scrubbing zone liquid toluene containing relatively volatile hydrocarbons absorbed therein.

2. A method for separatingrelatively vol tile hydrocarbons from a manufactured gas obtained by a process involving the pyrolytic decomposition of petroleum oil. whic comprises contacting said gas in a primary scrubbing zone at a temperature not, higher than about 0- C. .with liquid toluene to remove relatively volatile hydrocarbons by absorption in said toluene; pass-f above, the temperatures of the gas streamsenf tering the respective towers inorder to prevent The vaporous products leaving the stripping 40 zones by means of conduits lil and I6 may be separated and refined in any apparatus vsuited to the purpose. V

Make-up scrubbing media may be introduced into the system as shown at 20 and 2|. *Other scrubbing media might be substituted' for straw-oil such as other petroleum fractions For other absorbent oils of relatively low volatility.- I

It will be 'understood that the foregoing is by way of illustration and that changes, omissions, additions, substitutions,y and/or modications might be made within the scope of the claims without departing from the spirit of the inven- .Iclam:

1. A method ,for separating relatively volatile hydrocarbons 'from manufactured gas, which comprises cooling said, gas to a temperature suf- Iiciently low to effect-the condensation of at leastA the major portion of benzene hydrocarbons present, and including the condensation of at leastl the major portion of the benzene; separating condensed material from the gas; contacting the gas in' a 'primary scrubbing zone with liquid ing the scrubbed gas mixture containing toluene vapor taken up from said liquid toluene into secondary scrubbing zone; contacting sai scrubbed gas mixture in said secondary sc bbing zone with an absorbent oil relatively less volatile than said toluene to scrub out toluene from the gas mixture; withdrawing from said secondary scrubbing zone the residual gas mixture and the absorbent oil containing toluene absorbed therein; and withdrawing from said primary scrubbing zone liquid toluene containing relatively volatile hydrocarbons absorbed therein. 3. A method for continuously separating C4 and Cshydrocarbons from a gas mixture resulting from a process involving the'pyrolytic decomposition of petroleum oil, lwhich comprises contacting said gas mixture in a lirst scrubbing` zone at a temperaturenot higher than about 0 C.,wth liquid toluene to remove C4 and Cs hydrocarbons vfrom said gas mixture by absorption in said toluene; withdrawing from said rst scrubbing .zone the scrubbed gas mix ure containing toluene vapor taken/ up from said liquid toluene; contacting said scrubbed gas mixture in a second scrubbing'zone with a petroleum oil fraction having a boiling range of about 205 to 370 C. to remove toluene vapor from said gas mixture by absorption in said petroleum oil fraction; withdrawing the residual gas mixture from said second scrubbing zone; withdrawing from each of said scrubbing zones the respective liquid absorption media containing hydrocarbon constituents absorbed therein; and passing-said liquid absorption media to separate stripping zones and heating said liquid absorption media to separate I EDWIN L. HALL. 

